CN103708498B - A kind of high skeleton iron content Fe-SAPO-34 molecular sieve and preparation method thereof - Google Patents
A kind of high skeleton iron content Fe-SAPO-34 molecular sieve and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of high skeleton iron content Fe SAPO 34 molecular sieve and preparation method thereof, overcomes framework metal content in metal-modified SAPO 34 molecular sieve of the preparation reported in previous literature relatively low, the problem that catalysis activity is low when methanol to olefins reaction.Provide a kind of synthetic method with high skeleton iron content Fe SAPO 34 molecular sieve.It is high that the method has prepared SAPO 34 framework of molecular sieve iron atom content, the feature that catalysis activity is good, has preferable prospects for commercial application.
Description
Technical field
The invention belongs to the preparation method of a kind of molecular sieve, particularly relate to a kind of high skeleton iron content
Fe-SAPO-34 molecular sieve and preparation method thereof.
Background technology
SAPO-34 molecular sieve is the SAPO-n Series Molecules that UCC company of the U.S. synthesized first in nineteen eighty-two
A member in sieve, has class chabazite structure, has moderate acid and good heat stability and hydro-thermal
Stability, reveals the catalytic performance of excellence due to it to methanol oxidation preparing low-carbon olefins reaction table and enjoys
Pay close attention to.It has CHA structure and moderate acidity, shows excellence in methanol-to-olefins (MTO) technology
Catalytic performance and come into one's own.CHA includes 8 ring aperture composition elliposoidal cage and three-dimensional open-frameworks.
The catalytic performance of SAPO molecular sieve and structure have much relations, in order to expand applying of SAPO molecular sieve
Performance, is modified SAPO molecular sieve improving the focus that its catalytic performance is current research.
Add a certain metallic element in building-up process, with the Al atom replaced in skeleton, skeleton just produces
Having given birth to strong redox center, the quantity at reduction center increases with the raising of skeleton metal atom.This
During the character of sample makes hetero atom replacement aluminum phosphate be widely used in multi-catalytic, Thomas et al. exists
Hetero atom replaces aluminum phosphate and has done intensive research as catalyst aspect, and is used as single with regard to MAPO
Substantial amounts of article has been delivered in the application subject study of some solid catalyst.Document reports, adds hetero atom
SAPO-34 molecular sieve catalytic methanol to olefins reaction after metal-modified, can be effectively improved conversion ratio and
Selectivity to lighter hydrocarbons.It is modified generally comprising in-situ synthesis and dipping to molecular sieve by hetero atom
Method two kinds.Wherein the molecular sieve of the MeSAPO-34 containing hetero atom metal prepared by in-situ synthesis can urged
The aspects such as agent surface acidity, grain size, pore structure change.
Inui and Kang etc. report, SAPO-34 molecular sieve catalytic MTO reaction modified for Ni can obtain
The highest yield of ethene, can reach 90% to the selectivity of ethylene.
Li etc. report, the Fe-MCM-41 molecular sieve containing high skeleton iron in catalysis of phenol hydrogenation reaction,
What its catalysis specific activity Fe2O3 loaded catalyst activity is significantly increased, and with skeleton iron content
Increase and improve.
CN1704390, by using metallic element Zn to be modified SAPO-34, obtains Zn-SAPO-34
Molecular sieve, and as the catalyst of methanol-to-olefins, reaction under certain condition generates alkene.By
In the impact that SAPO-34 framing structure and pore structure are caused by the addition of metallic element Zn, improve point
The son sieve selectivity to low-carbon alkene, the overall selectivity of light hydrocarbon is more than 90%, and it is little that the response time reaches 6
Time.
CN102744102A is disclosed one and is modified SAPO-34 molecular sieve by infusion process, obtains
The catalyst of area load metal-oxide.Use metal-modified SAPO-34 molecular sieve catalyst
Producing ethylene by ethanol dehydration, have that ethanol conversion is high, ethylene selectivity is good, feed ethanol in the reaction
The feature that concentration is high, the air speed of ethanol is high and reaction temperature is low, thus improve the productivity of ethylene.
Summary of the invention
The problem to be solved in the present invention be to provide a kind of high skeleton iron content Fe-SAPO-34 molecular sieve and
Preparation method, overcomes hetero atom tenor in the metal-modified SAPO-34 molecular sieve of existing preparation
Relatively low, that catalysis activity is low when MTO reacts problem.
For solving above-mentioned technical problem, the invention the technical scheme is that a kind of high skeleton iron contains
Amount Fe-SAPO-34 molecular sieve, the preparation method of this molecular sieve is directly will be a large amount of for source of iron with Complexing Iron
Iron atom is incorporated in framework of molecular sieve, prepares the SAPO-34 molecular sieve of high skeleton iron content, its bone
The content of frame iron atom equals to or higher than 15wt%.
Preferably, the average pore size of described SAPO-34 molecular sieve is 0.40～0.60nm, is preferably
0.48～0.52nm.
Preferably, the specific surface area of described SAPO-34 molecular sieve is more than 480m2/g。
Present invention also offers one and prepare high skeleton iron content Fe-SAPO-34 molecular sieve as above
Method, including following preparation process,
(1), by a certain amount of silicon source, phosphorus source, aluminum source, water, source of iron, template at 10-70 DEG C
Under be mixed to get homogeneous colloids, wherein Al2O3: SiO2: P2O5: H2O: template: the mol ratio of source of iron
Example is 0.05-2:0.05-2:50-200:2-10:1-20；It is preferably Al2O3: SiO2: P2O5:
H2O: template: the molar ratio of source of iron is 0.5-1:0.5-1:100-150:5-8:10-15:5-10；
(2) homogeneous colloids, by step (1) obtained, continues stirring 3 hours at 10-70 DEG C,
Then under 0-180 DEG C of self-generated pressure hydrothermal condition, crystallization 12-120 hour, obtain the product after crystallization
Thing；
(3), by the product after crystallization through by the product after crystallization through sucking filtration, wash, dry,
Roasting obtains molecular sieve finished product.
Preferably, the one during described source of iron is the potassium ferricyanide, potassium ferrocyanide.
Preferably, used template is di-n-propylamine, diisopropylamine, one or both in diethylamine
Above.
Preferably, described silicon source is the one in aerosil, waterglass, tetraethyl orthosilicate or two
More than Zhong, source of aluminium is boehmite, and phosphorus source is orthophosphoric acid.
Preferably, the drying in step (3) is to dry 3-8 hour at 100-130 DEG C.
Preferably, described sucking filtration, washing process refer to add deionized water wash filter while sucking filtration
Cake, the pH to filtrate is 7.
Preferably, described roasting be under conditions of 1 DEG C/min temperature programming to 350 DEG C-700 DEG C guarantors
Temperature 5 hours.
The invention has the advantage that with good effect: SAPO-34 molecular sieve prepared by the present invention,
With Complexing Iron as source of iron, a large amount of iron atoms are introduced directly in framework of molecular sieve, improve
The content of skeleton iron in Fe-SAPO-34, improves Fe-SAPO-34 used in methanol to olefins reaction and divides
Sub-sieve catalyst, improves the acidity of catalyst, strengthens its selectivity and activity.Both SAPO-34 had been maintained
The pore passage structure of molecular sieve rule, the feature of higher specific surface area has again high tenor, fully
The metallic character that hetero atom itself is had, the catalytic of the molecular sieve synthesized by further modulation are played
Can, expand its range of application, it will become the aspect performance such as catalytic cracking, catalysis oxidation, isomerization
Excellent catalysis material.Simultaneously because the present invention synthesis Fe-SAPO-34 molecular sieve in iron content very
Height, makes aperture increase accordingly.And the distribution of iron atom is the most uniform, is adding the B of molecular sieve
While Suan JiLSuan center, the acid centre dispersibility also making molecular sieve is more preferable, has the strongest diving
Using value.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the high skeleton iron content Fe-SAPO-34 molecular sieve of embodiment two in the present invention.
Fig. 2 is the SEM figure of the high skeleton iron content Fe-SAPO-34 molecular sieve of embodiment two in the present invention.
Fig. 3 is the ferrum element of the high skeleton iron content Fe-SAPO-34 molecular sieve of embodiment two in the present invention
EPR figure.
Detailed description of the invention
In the embodiment of the present invention, source of iron used is as a example by the potassium ferricyanide and potassium ferrocyanide.Template used
As a example by diethylamine, silicon source used as a example by aerosil and tetraethyl orthosilicate, aluminum source used
As a example by boehmite；Phosphorus source used is as a example by 85% orthophosphoric acid；Water used is deionized water；
Reagent used all uses analytical reagent；It is to survey with powder diffraction that the X-ray diffraction of gained finished product measures
Examination, instrument is Rigaku D/max-RA type X-ray diffractometer, voltage 30kV, electric current 30mA,
Sweep limits 3-70 °；In gained finished product, the content of ferrum measures through X-ray fluorescence spectra, instrument
For Philip Magix-601 fluorescence diffractometer；SEM tests at Jeol Ltd. JSM-35C
Carry out on type scanning electron microscope instrument, SEI25Kv, 1.0 × 10-11A；Electron paramagnetic spectrum is at Brooker
ER041MR carries out testing, and magnetic field intensity is 9.44GHz.
Embodiment one
10g phosphoric acid and 10g tetraethyl orthosilicate are joined in 60ml deionized water, stirs 15min
After, add 11g K4Fe(CN)6After continuing stirring 60min, add 8ml diethylamine, react 3 hours
After transfer the solution in the autoclave of polytetrafluoro liner, crystalline state crystallization at self-generated pressure 160 DEG C
72 hours.Then by sample sucking filtration, it is washed with deionized to neutrality, at 100 DEG C, is dried 6 little
Time.With 1 DEG C of min-1Rate program be warming up to 550 DEG C, be incubated 5h, remove template.
Embodiment two
10g phosphoric acid and 12.1g tetraethyl orthosilicate are joined in 60ml deionized water, stirs 15min
After, add 11g K4Fe(CN)6After continuing stirring 60min, adding 10ml diethylamine, reaction 3 is little
Transferring the solution in the autoclave of polytetrafluoro liner time after, at self-generated pressure 160 DEG C, crystalline state is brilliant
Change 72 hours.Then by sample sucking filtration, it is washed with deionized to neutrality, at 100 DEG C, is dried 6
Hour.With 1 DEG C of min-1Rate program be warming up to 550 DEG C, be incubated 5h, remove template.
Embodiment three
8g phosphoric acid and 12.1g tetraethyl orthosilicate are joined in 60ml deionized water, stirs 15min
After, add 11g K4Fe(CN)6After continuing stirring 60min, adding 10ml diethylamine, reaction 3 is little
Transferring the solution in the autoclave of polytetrafluoro liner time after, at self-generated pressure 180 DEG C, crystalline state is brilliant
Change 72 hours.Then by sample sucking filtration, it is washed with deionized to neutrality, at 100 DEG C, is dried 6
Hour.With 1 DEG C of min-1Rate program be warming up to 550 DEG C, be incubated 5 hours, remove template.
Embodiment four
10g phosphoric acid and 3g silicon dioxide are joined in 60ml deionized water, after stirring 15min,
Add 11g K4Fe(CN)6After continuing stirring 60min, add 10ml diethylamine, after reacting 3 hours
Transfer the solution in the autoclave of polytetrafluoro liner, crystalline state crystallization 24 at self-generated pressure 160 DEG C
Hour.Then by sample sucking filtration, it is washed with deionized to neutrality, is dried 6 hours at 100 DEG C.
It is warming up to 550 DEG C with the rate program of 1 DEG C of min-1, is incubated 5h, remove template.
Embodiment five
10g phosphoric acid and 12.1g tetraethyl orthosilicate are joined in 60ml deionized water, stirs 15min
After, add 11g K3Fe(CN)6After continuing stirring 60min, adding 10ml diethylamine, reaction 3 is little
Transferring the solution in the autoclave of polytetrafluoro liner time after, at self-generated pressure 160 DEG C, crystalline state is brilliant
Change 72 hours.Then by sample sucking filtration, it is washed with deionized to neutrality, at 100 DEG C, is dried 6
Hour.It is warming up to 550 DEG C with the rate program of 1 DEG C of min-1, is incubated 5h, remove template.
Embodiment six
10g phosphoric acid and 2.6g silicon dioxide are joined in 60ml deionized water, after stirring 15min,
Add 11g K3Fe(CN)6After continuing stirring 60min, add 10ml diethylamine, after reacting 3 hours
Transfer the solution in the autoclave of polytetrafluoro liner, crystalline state crystallization 72 at self-generated pressure 180 DEG C
Hour.Then by sample sucking filtration, it is washed with deionized to neutrality, is dried 6 hours at 100 DEG C.
With 1 DEG C of min-1Rate program be warming up to 550 DEG C, be incubated 5h, remove template.
High skeleton iron content Fe-SAPO-34 molecular sieve embodiment two prepared carries out X-ray respectively and spreads out
Penetrating mensuration, SEM test, EPR test, result is as shown in Figure 1, Figure 2, Figure 3 shows.The survey of XRD
Test result shows, framework of molecular sieve still maintains preferably crystallization after introducing substantial amounts of iron atom
Degree.The scanning electron microscope of sample i.e. SEM result shows, molecular sieve has preferable crystal morphology, crystal
Surface does not has metal-oxide.The EPR data of sample show, the middle iron atom of sample is all
Presented in four-coordination, say, that the ferrum in sample has all entered in framework of molecular sieve.
High skeleton iron content Fe-SAPO-34 molecular sieve embodiment one～embodiment six prepared enters respectively
Row X-ray fluorescence spectra measures, and measures the content of ferrum, and its iron content is all higher than 15wt%.
Arranging comparative example 1, this comparative example is for illustrating the catalytic of unmodified SAPO-34 molecular sieve
Energy.
Unmodified SAPO-34 molecular sieve is used for catalysis methanol olefine reaction, reacts at normal pressure even
Afterflow is moved and is carried out on fixed bed reactors.0.2g is loaded in the quartz tube reactor that internal diameter is 10mm
Catalyst.Reaction condition is: with air speed as 2.0h-1It is passed through methanol-N2-H2(three's mol ratio is O
1:3:5) reaction mixture gas.Concrete grammar is as follows: 80 DEG C of water-baths, in airtight there-necked flask, adds 50ml
The tert-butyl alcohol, 8g Ketohexamethylene, 15g25% ammonia, 10g hydrogen peroxide, the response time is 1h.By comparative example
1 product obtained, with conversion ratio and the selectivity of cyclohexanone-oxime of Agilent 7890 chromatographic determination Ketohexamethylene.
By Fe-SAPO-34 molecular sieve modified to embodiment one～embodiment six according to the method for comparative example 1
Substitute unmodified SAPO-34 molecular sieve, for methanol to olefins reaction, products therefrom Agilent
The conversion ratio of 7890 chromatographic determination methanol and the selectivity of low-carbon alkene, concrete outcome is shown in Table 1.
Wherein, the methanol of the selectivity of low-carbon alkene=change into methanol/conversion that low-carbon alkene is consumed
Amount × 100%
Table 1
| Group | Selectivity % |
| Comparative example 1 | 94 |
| Embodiment 1 | 95.2 |
| Embodiment 2 | 97.1 |
| Embodiment 3 | 96.5 |
| Embodiment 4 | 95.7 |
| Embodiment 5 | 95.3 |
| Embodiment 6 | 96.5 |
As seen from the above table, the Fe-SAPO-34 molecular sieve prepared through the present invention for methanol to olefins reaction,
The selectivity of low-carbon alkene all more than 95%, be these results suggest that, the high skeleton iron content of preparation by it
Fe-SAPO-34 molecular sieve catalytic performance is improved significantly.
Above the embodiment of the invention is described in detail, but described content has been only present invention wound
The preferred embodiment made, it is impossible to be considered the practical range for limiting the present invention.All according to the invention
Equalization change and the improvement etc. that scope is made, within all should still belonging to this patent covering scope.
Claims (10)
1. one kind high skeleton iron content Fe-SAPO-34 molecular sieve, it is characterised in that: the system of this molecular sieve
Preparation Method is directly to be incorporated in framework of molecular sieve by a large amount of iron atoms with Complexing Iron for source of iron, prepares processus styloideus radii
The SAPO-34 molecular sieve of frame iron content, the content of its skeleton iron atom equals to or higher than 15wt%；Institute
The average pore size stating SAPO-34 molecular sieve is 0.40～0.60nm, the ratio of described SAPO-34 molecular sieve
Surface area is more than 480m2/g。
High skeleton iron content Fe-SAPO-34 molecular sieve the most as claimed in claim 1, its feature exists
In: the average pore size of described SAPO-34 molecular sieve is 0.48～0.52nm.
3. the side preparing high skeleton iron content Fe-SAPO-34 molecular sieve as claimed in claim 1
Method, it is characterised in that: include following preparation process,
(1), by a certain amount of silicon source, phosphorus source, aluminum source, water, source of iron, template at 10-70 DEG C
It is mixed to get homogeneous colloids, wherein Al2O3: SiO2: P2O5: H2O: template: the mol ratio of source of iron
Example is 0.05-2:0.05-2:50-200:2-10:1-20；
(2) homogeneous colloids, by step (1) obtained, continues stirring 3 hours at 10-70 DEG C,
Then under 0-180 DEG C of self-generated pressure hydrothermal condition, crystallization 12-120 hour, obtain the product after crystallization
Thing；
(3), by the product after crystallization through sucking filtration, wash, dry, roasting obtains molecular sieve finished product.
4. the method preparing high skeleton iron content Fe-SAPO-34 molecular sieve as claimed in claim 3,
It is characterized in that: described source of iron is the one in the potassium ferricyanide, potassium ferrocyanide.
5. the method preparing high skeleton iron content Fe-SAPO-34 molecular sieve as claimed in claim 3,
It is characterized in that: used template is di-n-propylamine, diisopropylamine, one or both in diethylamine
Above.
6. the method preparing high skeleton iron content Fe-SAPO-34 molecular sieve as claimed in claim 3,
It is characterized in that: described silicon source is the one in aerosil, waterglass, tetraethyl orthosilicate or two
More than Zhong, source of aluminium is boehmite, and phosphorus source is orthophosphoric acid.
7. the method preparing high skeleton iron content Fe-SAPO-34 molecular sieve as claimed in claim 3,
It is characterized in that: the drying in step (3) is to dry 3-8 hour at 100-130 DEG C.
8. the method preparing high skeleton iron content Fe-SAPO-34 molecular sieve as claimed in claim 3,
It is characterized in that: described sucking filtration, washing process refer to add deionized water wash filter while sucking filtration
Cake, the pH to filtrate is 7.
9. the method preparing high skeleton iron content Fe-SAPO-34 molecular sieve as claimed in claim 3,
It is characterized in that: described roasting be under conditions of 1 DEG C/min temperature programming to 350 DEG C-700 DEG C guarantors
Temperature 5 hours.
10. the method preparing high skeleton iron content Fe-SAPO-34 molecular sieve as claimed in claim 3,
It is characterized in that: in described step (1), Al2O3: SiO2: P2O5: H2O: template: source of iron
Molar ratio be 0.5-1:0.5-1:100-150:5-8:10-15:5-10.
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| CN104709921B (en) * | 2015-03-10 | 2016-08-24 | 中国天辰工程有限公司 | A kind of micro passage reaction and the method using its production Magnetic titanium silicon molecular sieve |
| CN107855132B (en) * | 2017-11-07 | 2020-02-18 | 大连理工大学 | Method for preparing Fe/SAPO-34 catalyst by utilizing SAPO-34 molecular sieve and application thereof |
| CN109485068B (en) * | 2018-08-30 | 2020-11-13 | 南京大学 | Two-dimensional ultrathin Me-SAPO-34 molecular sieve sheet material and preparation method thereof |
| CN109317193A (en) * | 2018-11-12 | 2019-02-12 | 上海第二工业大学 | A kind of application of Fe-SAPO-34 catalyst in methyl stearate synthesis |
| CN112694100B (en) * | 2019-10-22 | 2023-01-24 | 中国石油化工股份有限公司 | Fe-ZSM-5 molecular sieve, preparation method and application thereof |
| CN111686797A (en) * | 2020-07-09 | 2020-09-22 | 常州工程职业技术学院 | Fe-SAPO-34 molecular sieve catalyst, preparation method and application |
| CN114210364A (en) * | 2021-11-17 | 2022-03-22 | 青岛科技大学 | Iron-loaded functionalized SAPO-34 molecular sieve and preparation method and application thereof |
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| CN1966149A (en) * | 2005-11-17 | 2007-05-23 | 中国科学院大连化学物理研究所 | Catalyst for chloromethane conversion to produce low carbon olefin and its uses |
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